CN107029775B - Zirconium-oxygen-nitrogen-cerium solid solution and preparation method and application thereof - Google Patents
Zirconium-oxygen-nitrogen-cerium solid solution and preparation method and application thereof Download PDFInfo
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- 239000006104 solid solution Substances 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title abstract description 11
- NUYWKZCDZBRUMP-UHFFFAOYSA-N [Ce].[N].[O].[Zr] Chemical compound [Ce].[N].[O].[Zr] NUYWKZCDZBRUMP-UHFFFAOYSA-N 0.000 title description 4
- 238000004519 manufacturing process Methods 0.000 claims abstract description 32
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 29
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000001257 hydrogen Substances 0.000 claims abstract description 29
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 29
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 28
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims abstract description 28
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 230000001699 photocatalysis Effects 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 9
- 238000000354 decomposition reaction Methods 0.000 claims abstract description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 16
- 239000001301 oxygen Substances 0.000 claims description 16
- 229910052760 oxygen Inorganic materials 0.000 claims description 16
- 239000000243 solution Substances 0.000 claims description 16
- FVAUCKIRQBBSSJ-UHFFFAOYSA-M sodium iodide Chemical compound [Na+].[I-] FVAUCKIRQBBSSJ-UHFFFAOYSA-M 0.000 claims description 15
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 claims description 10
- 239000002245 particle Substances 0.000 claims description 9
- RCFVMJKOEJFGTM-UHFFFAOYSA-N cerium zirconium Chemical compound [Zr].[Ce] RCFVMJKOEJFGTM-UHFFFAOYSA-N 0.000 claims description 7
- 239000013078 crystal Substances 0.000 claims description 5
- 239000002105 nanoparticle Substances 0.000 claims description 5
- 235000009518 sodium iodide Nutrition 0.000 claims description 5
- 229910052979 sodium sulfide Inorganic materials 0.000 claims description 4
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 claims description 4
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 4
- 235000010265 sodium sulphite Nutrition 0.000 claims description 4
- 229910052697 platinum Inorganic materials 0.000 claims description 3
- 239000000463 material Substances 0.000 abstract description 14
- 238000006243 chemical reaction Methods 0.000 abstract description 4
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 239000012467 final product Substances 0.000 abstract 1
- 239000007789 gas Substances 0.000 abstract 1
- 238000001027 hydrothermal synthesis Methods 0.000 abstract 1
- 239000000543 intermediate Substances 0.000 abstract 1
- 239000002994 raw material Substances 0.000 abstract 1
- 239000011941 photocatalyst Substances 0.000 description 13
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 12
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium dioxide Chemical compound O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 description 8
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 description 8
- 230000007547 defect Effects 0.000 description 7
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- UMZZZCGXUOLFFT-UHFFFAOYSA-K cerium(3+);trinitrite Chemical compound [Ce+3].[O-]N=O.[O-]N=O.[O-]N=O UMZZZCGXUOLFFT-UHFFFAOYSA-K 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 229940119177 germanium dioxide Drugs 0.000 description 4
- 239000010453 quartz Substances 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 238000012512 characterization method Methods 0.000 description 3
- 230000001678 irradiating effect Effects 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 238000006303 photolysis reaction Methods 0.000 description 2
- 230000015843 photosynthesis, light reaction Effects 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- 229910002937 BaTaO2N Inorganic materials 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 229910003071 TaON Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000004931 aggregating effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 238000013032 photocatalytic reaction Methods 0.000 description 1
- -1 polytetrafluoroethylene Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
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- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910001428 transition metal ion Inorganic materials 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- B01J35/39—
-
- B01J35/40—
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/04—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of inorganic compounds, e.g. ammonia
- C01B3/042—Decomposition of water
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/02—Processes for making hydrogen or synthesis gas
- C01B2203/0266—Processes for making hydrogen or synthesis gas containing a decomposition step
- C01B2203/0277—Processes for making hydrogen or synthesis gas containing a decomposition step containing a catalytic decomposition step
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
- C01B2203/1047—Group VIII metal catalysts
- C01B2203/1064—Platinum group metal catalysts
- C01B2203/107—Platinum catalysts
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Abstract
The invention discloses a new material of zirconium oxynitride cerium, a preparation method and application thereof. According to the invention, intermediates cerium germanate and zirconium germanate are synthesized by a hydrothermal method, and then the final product of the nanometer-sized zirconium oxynitride cerium Ce0.3Zr0.7O1.88N0.12 with a sub-stoichiometric ratio is obtained by a high-temperature gas phase reduction method. The method has the advantages of simple operation, simple process equipment, easily obtained raw materials, lower preparation cost, short reaction period and high repeatability. The material has excellent hydrogen production performance when being applied to a photocatalytic hydrogen production reaction, and can be used as a Z system hydrogen production end material to realize the decomposition of pure water by visible light. The novel solid solution material of the zirconium oxynitride cerium has very important application in the fields of environmental science and solar energy conversion.
Description
Technical Field
The invention belongs to a nitrogen oxygen zirconium cerium Ce0.3Zr0.7O1.88N0.12 nano material with a sub-stoichiometric ratio, which is formed by aggregating small 5-30 nano particles into spherical large particles, has excellent performance in the aspect of photocatalytic hydrogen production, and has potential application performance in the fields of other energy development and environmental protection.
Background
The search for suitable semiconductor materials as stable, efficient and visible light responsive photocatalysts has been a hotspot. Generally, the photocatalysts studied so far contain transition metal ions of d0 electronic configuration (e.g., Ti4+, Nb5+ and Ta5+) or d10 electronic configuration (e.g., In3+, Ga3+ and Ge4 +). The top of the valence band of these metal oxides containing d0 or d10 metal ions is usually composed of the 2p orbital of O, so these metal oxides have a wide forbidden band width and thus do not have photocatalytic performance under visible light. Because the 2p state of N is more electrically positive than the 2p state of O, the top of the valence band of these oxide photocatalysts can be increased by the introduction of the N element. Thus, many nitrogen oxides have been studied as visible light-responsive photocatalysts, such as: TaON, BaTaO2N, SrNbO2N, TiO2N, and the like. However, these oxynitrides are relatively unstable, probably due to the introduction of the N element, which causes a large number of bulk and surface defects to occur, resulting in slower charge separation efficiency and faster charge and efficiency. However, there are also reports that: bulk defects can serve as the sum-and-center of photogenerated electron holes, whereas surface and subsurface oxygen defects can serve as reactive sites for photocatalytic reactions or facilitate charge separation. In addition, the surface defects can be used as capture centers of photogenerated electron holes, thereby playing roles in promoting electron transfer and inhibiting charge attachment. It should be noted that the concentration of these material surface defects can be theoretically adjusted by adjusting the geometry and electronic structure of the material. However, it remains a challenge to adjust the concentration of surface defects so that nitrogen oxides act as stable and efficient photocatalysts.
In the invention, a novel Ce0.3Zr0.7O1.88N0.12 solid solution material with appropriate surface defect concentration is designed to be used as a stable, efficient and visible light-responsive hydrogen production photocatalyst. Moreover, the material is used as a hydrogen production end to construct a Z system, so that the decomposition of pure water by visible light can be realized. Combining structural characterization and theoretical calculations, we attributed the excellent photocatalytic activity and stability of ce0.3zr0.7o1.88n0.12 solid solution materials to the increased separation rate of photogenerated carriers due to surface and subsurface oxygen vacancies.
disclosure of Invention
In view of the above problems, the present invention aims to provide a nano zirconium oxynitride cerium, a preparation method and an application thereof, wherein the preparation method is simple and the cost is low. The prepared nano material has excellent photocatalytic hydrogen production performance. The synthesis process does not need complex instruments, is simple to operate and is beneficial to large-scale production.
In order to achieve the purpose, the invention adopts the following technical scheme:
the molecular formula of the solid solution is Ce0.3Zr0.7O1.88N0.12, the size of the solid solution is 5-30 nanometers, small nano particles are agglomerated into spherical large particles, and the crystal form of the solid solution is a cubic phase.
A preparation method of a zirconium oxynitride cerium solid solution comprises the following steps:
(1) Adding cerium nitrite (0.1-0.9 mmol), zirconium nitrate (0.9-0.1 mmol), germanium dioxide (0.1-1.0 mmol), citric acid (0.1-1.0 mmol) and 30-50 ml of deionized water solution into a hydrothermal kettle with a polytetrafluoroethylene lining, reacting at 150-250 ℃ for 12-48 hours, and taking out;
(2) and (2) putting 50-200 mg of the product obtained in the step (1) into a quartz ark in a tube furnace, introducing sufficient ammonia gas at the rate of 0.02-0.08L/min, and reacting for 6-30 hours to obtain a solid solution Ce0.3Zr0.7O1.88N0.12 with the size of 5-30 nanometers, wherein the small nanoparticles are agglomerated into spherical large particles and the crystal form is a cubic phase.
An application of nano zirconium oxynitride cerium in preparing hydrogen by decomposing water under photocatalysis.
The application method comprises the following steps: adding 30-200 mg of cerium zirconium oxynitride into 0.1-0.35 mol/L Na2S and 0.1-0.25 mol/L Na2SO3 solutions, wherein hydrogen production amounts of visible light or full-band light for 24 hours are 10-25 micromoles and 80-120 micromoles respectively; 30-200 mg of 2% RuO 2-loaded zirconium oxynitride cerium solid solution and 30-200 mg of 1% Pt-loaded tungsten trioxide are added into 1 mmol/L sodium iodide solution, the oxygen production and oxygen production rates after 24 hours of visible light irradiation are respectively 1.1-3.3 micromoles and 0.6-1.7 micromoles, and the oxygen production and oxygen production rates after 24 hours of all-band light irradiation are respectively 6.2-10.8 micromoles and 3.1-5.4 micromoles.
The invention has the beneficial effects that:
(1) The nano-size zirconium oxynitride cerium solid solution material Ce0.3Zr0.7O1.88N0.12 is synthesized by a simple two-step method, the synthesis method is simple, the operation is simple and convenient, the condition is mild, the purity of a target product is high, the method is safe and nontoxic, and the nano-size zirconium oxynitride cerium solid solution material can be synthesized in a large scale;
(2) The nano-size zirconium oxynitride cerium solid solution Ce0.3Zr0.7O1.88N0.12 is used as the hydrogen production photocatalyst, and the result shows that the photocatalyst has better photocatalytic hydrogen production performance and better stability. The hydrogen production amounts of visible light or full-wave band light irradiation for 24 hours are respectively 19 micromoles and 102 micromoles, and the stability is 24 days;
(3) In the preparation process, all reagents are commercial products and do not need further treatment;
(4) The synthesis method is simple, and the obtained material is easy to apply, is favorable for popularization and application in industrial production, and is used for hydrogen evolution materials in chlor-alkali industry, water photolysis process, solar water photolysis hydrogen production and Z system.
Drawings
FIG. 1 is an electron photograph of zirconium oxynitride cerium prepared in example 1;
FIG. 2 is a graph showing the performance of zirconium oxynitride cerium prepared in example 1 as a hydrogen-generating photocatalyst;
FIG. 3 is a diagram of pure water produced by photocatalytic decomposition using zirconium oxynitride cerium prepared in example 1 as a hydrogen producing end of a Z system;
FIG. 4 is an X-ray diffraction pattern of zirconium oxynitride cerium prepared in example 1;
FIG. 5 is a transmission electron microscope photograph of zirconium oxynitride cerium prepared in example 1;
FIG. 6 is a scanning electron micrograph of cerium zirconium oxynitride prepared in example 1.
Detailed Description
the following detailed description of the present invention will be made with reference to the accompanying drawings and examples, but the scope of the present invention should not be limited thereby.
The "ranges" disclosed herein are in the form of lower and upper limits. There may be one or more lower limits, and one or more upper limits, respectively. The given range is defined by the selection of a lower limit and an upper limit. The selected lower and upper limits define the boundaries of the particular range. All ranges that can be defined in this manner are inclusive and combinable, i.e., any lower limit can be combined with any upper limit to form a range. For example, ranges of 60-120 and 80-110 are listed for particular parameters, with the understanding that ranges of 60-110 and 80-120 are also contemplated. Furthermore, if the minimum range values 1 and 2 are listed, and if the maximum ranges 3, 4, and 5 are listed, the following ranges are all contemplated: 1-2, 1-4, 1-5, 2-3, 2-4 and 2-5.
in the present invention, unless otherwise stated, the numerical range "a-b" represents a shorthand representation of any combination of real numbers between a and b, where a and b are both real numbers. For example, a numerical range of "0 to 5" indicates that all real numbers between "0 to 5" have been listed herein, and "0 to 5" is only a shorthand representation of the combination of these numbers.
In the present invention, all embodiments and preferred embodiments mentioned herein may be combined with each other to form a new technical solution, if not specifically stated.
In the present invention, all the technical features mentioned herein and preferred features may be combined with each other to form new technical solutions, if not specifically mentioned.
The preferred embodiments of the present invention will be described in detail with reference to the following examples, but it should be understood that those skilled in the art can reasonably change, modify and combine the examples to obtain new embodiments without departing from the scope defined by the claims, and that the new embodiments obtained by changing, modifying and combining the examples are also included in the protection scope of the present invention.
Example 1
step one, preparation of nitrogen oxygen zirconium cerium solid solution
Adding cerium nitrite (0.3 mmol), zirconium nitrate (0.7 mmol), germanium dioxide (0.5 mmol), citric acid (0.5 mmol) and 30 ml of deionized water solution into a polytetrafluoroethylene-lined hydrothermal kettle, reacting for 24 hours at 200 ℃, and taking out; and (2) putting 50-200 mg of the product obtained in the step (1) into a quartz ark in a tube furnace, introducing sufficient ammonia gas at 0.04L/min, and reacting for 10 hours to obtain a solid solution Ce0.3Zr0.7O1.88N0.12 with the size of 5-30 nanometers, wherein small nano particles are agglomerated into spherical large particles and the crystal form is a cubic phase.
Step two, performance characterization test
adding 50 mg of cerium zirconium oxynitride into a solution of 0.35 mol/L Na2S and 0.25 mol/L Na2SO3, irradiating for 24 hours by visible light or full-wave-band light, vacuumizing, and repeating the above operations for 24 days in total; 50 mg of a 2% RuO 2-supported zirconium oxynitride cerium solid solution and 50 mg of 1% Pt-supported tungsten trioxide were added to a 1 mmol/L sodium iodide solution, irradiated with visible light or full-band light for 24 hours, and then evacuated to repeat the above operations for a total reaction time of 72 hours.
Fig. 1 is an electronic photograph of the product, and it can be seen that the prepared zirconium oxynitride cerium is a yellow-green powder.
FIG. 2 is a graph showing the performance of zirconium oxynitride cerium prepared in example 1 as a hydrogen generation photocatalyst. Wherein: curve 1 is a hydrogen production curve under test conditions of 50 ml of 0.35 mol/l Na2S and 0.25 mol/l Na2SO3 solution by using 50 mg of cerium zirconium oxynitride prepared in example 1 as a hydrogen production photocatalyst under full-band light irradiation. Curve 2 is the hydrogen production curve under visible light irradiation. As can be seen from fig. 2, the hydrogen production amounts of zirconium oxynitride cerium as a hydrogen production photocatalyst in visible light or full-band light irradiation for 24 hours were 19 micromoles and 102 micromoles, respectively. Meanwhile, the hydrogen yield at 24 days of the reaction is still not reduced, which indicates that the zirconium oxynitride cerium has very good stability.
FIG. 3 is a diagram showing photocatalytic decomposition of pure water with zirconium oxynitride cerium prepared in example 1 as the hydrogen generating end of the Z system. Wherein: curves H2 and O2 are hydrogen and oxygen production amounts obtained by adding 50 mg of a 2% RuO 2-loaded zirconium oxynitride cerium solid solution and 50 mg of 1% Pt-loaded tungsten trioxide to 1 mmol/l sodium iodide solution and irradiating the mixture under full-band light for 24 hours. Curves H2 'and O2' are hydrogen and oxygen production curves under visible light irradiation. The oxygen production by hydrogen and oxygen production after 24 hours of visible light irradiation are respectively 2.28 micromole and 1.11 micromole, and the oxygen production by hydrogen and oxygen production after 24 hours of full-wave band light irradiation are respectively 8.63 micromole and 4.11 micromole.
FIG. 4 is an X-ray diffraction pattern of the product identified as Ce0.3Zr0.7O1.88N0.12. The curve is the X-ray diffraction pattern of the prepared zirconium oxynitride cerium particles at the scanning speed of 3 degrees/min and the scanning range of 10 degrees to 80 degrees.
Fig. 5 is a transmission electron micrograph of example 1, and it is found by observing that the lattice line of the sample coincides with the lattice spacing of the ce0.3zr0.7o1.88n0.12 crystal form, demonstrating that the synthesized particle is ce0.3zr0.7o1.88n0.12.
FIG. 6 is a scanning electron microscope image of example 1, wherein the sample morphology is observed, and the small particles of 5-30 nm are agglomerated into spherical large particles.
Example 2
Step one, preparation of CexZr1-xO1.88N0.12(x is 0.1-0.9) solid solution
Adding cerium nitrite (x mmol), zirconium nitrate (1-x mmol), germanium dioxide (0.5 mmol), citric acid (0.5 mmol) and 30 ml of deionized water solution into a polytetrafluoroethylene-lined hydrothermal kettle, reacting for 24 hours at 200 ℃, and taking out; and (2) putting 50-200 mg of the product obtained in the step (1) into a quartz boat in a tube furnace, introducing sufficient ammonia gas at the rate of 0.04L/min, and reacting for 10 hours to obtain a solid solution CexZr 1-xO1.88N0.12.
Step two, performance characterization test
Adding 50 mg of zirconium cerium oxynitride into a 10% methanol solution, irradiating for 24 hours by visible light or full-wave band light, and then vacuumizing and repeating the above operations; 50 mg of a 2% RuO 2-supported zirconium oxynitride cerium solid solution and 50 mg of 1% Pt-supported tungsten trioxide were added to a 1 mmol/L sodium iodide solution, irradiated with visible light or full-band light for 24 hours, and then evacuated to repeat the above operations.
Example 3
Step one, preparation of Pt/Ce0.3Zr0.7O1.88N0.12 photocatalyst
Adding cerium nitrite (0.3 mmol), zirconium nitrate (0.7 mmol), germanium dioxide (0.5 mmol), citric acid (0.5 mmol) and 30 ml of deionized water solution into a polytetrafluoroethylene-lined hydrothermal kettle, reacting for 24 hours at 200 ℃, and taking out; and (2) putting 50-200 mg of the product obtained in the step (1) into a quartz ark in a tube furnace, introducing sufficient ammonia gas at the rate of 0.04L/min, and reacting for 10 hours to obtain a solid solution Ce0.3Zr0.7O1.88N0.12. Sintering 100 mg of the obtained zirconium-oxynitride-cerium solid solution and 2.1-10.5 mg of chloroplatinic acid (Pt and Ce0.3Zr0.7O1.88N0.12 mass ratio is 1-5%) in air at 400 ℃ for 3 hours, and taking out.
The above description is only a preferred embodiment of the present invention, and all equivalent changes and modifications made in accordance with the claims of the present invention should be covered by the present invention.
Claims (1)
1. The application of the zirconium oxynitride cerium solid solution is characterized in that the molecular formula of the zirconium oxynitride cerium solid solution is Ce0.3Zr0.7O1.88N0.12, the size is 5-30 nanometers, small nanoparticles are agglomerated into spherical large particles, and the crystal form is a cubic phase; the zirconium cerium oxynitride is used for preparing hydrogen by photocatalytic water decomposition; the application method comprises the following steps: adding 30-200 mg of cerium zirconium oxynitride into 0.1-0.35 mol/L Na2S and 0.1-0.25 mol/L Na2SO3 solutions, wherein hydrogen production amounts of visible light or full-band light for 24 hours are 10-25 micromoles and 80-120 micromoles respectively; 30-200 mg of 2% RuO 2-loaded zirconium oxynitride cerium solid solution and 30-200 mg of 1% Pt-loaded tungsten trioxide are added into 1 mmol/L sodium iodide solution, the oxygen production and oxygen production rates after 24 hours of visible light irradiation are respectively 1.1-3.3 micromoles and 0.6-1.7 micromoles, and the oxygen production and oxygen production rates after 24 hours of all-band light irradiation are respectively 6.2-10.8 micromoles and 3.1-5.4 micromoles.
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| CN201710229881.8A CN107029775B (en) | 2017-04-10 | 2017-04-10 | Zirconium-oxygen-nitrogen-cerium solid solution and preparation method and application thereof |
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